CN104555940B - Reduce the recovery technology of sulfur of sulfur dioxide (SO2) emissions - Google Patents

Reduce the recovery technology of sulfur of sulfur dioxide (SO2) emissions Download PDF

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CN104555940B
CN104555940B CN201310482966.9A CN201310482966A CN104555940B CN 104555940 B CN104555940 B CN 104555940B CN 201310482966 A CN201310482966 A CN 201310482966A CN 104555940 B CN104555940 B CN 104555940B
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sulfur
gas
ammonia
tail gas
hydrogenation
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CN104555940A (en
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刘爱华
刘剑利
梁颖杰
陶卫东
刘增让
许金山
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B01D53/523—Mixtures of hydrogen sulfide and sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
    • B01D53/8615—Mixtures of hydrogen sulfide and sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/102—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines

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Abstract

The invention belongs to technical field of sulfur recovery, be specifically related to a kind of recovery technology of sulfur reducing sulfur dioxide (SO2) emissions.Including thermal response unit, catalytic reaction unit and cleaning of off-gas unit, on the basis of traditional Crouse's+SCOT tail gas treatment process, add ammonia absorption tank, in ammonia absorption tank, cleaning of off-gas is removed H2S, it is ensured that H in cleaning of off-gas2S content is less than 5mg/m3；Deposed ammonia processes to sewage stripping device, can extract H respectively at sewage stripping device2S and ammonia, the H extracted2S returns sulfur recovery facility and carries out sulfur recovery, and the ammonia extracted returns ammonia water tank and recycles；Final sulphur unit flue gas SO2Concentration of emission can be down to 100mg/m3Hereinafter, meet the new environmental protection standard that will perform, provide a kind of small investment for newly-built sulphur unit, new method that operating cost is low.There is good absorbing effect, simple to operate, expense is low, environmental protection, the advantage of saving.

Description

Reduce the recovery technology of sulfur of sulfur dioxide (SO2) emissions
Technical field
The invention belongs to technical field of sulfur recovery, be specifically related to a kind of sulphur recovery work reducing sulfur dioxide (SO2) emissions Skill.
Background technology
Along with the development of society, problem of environmental pollution has become the restraining factors of rapid economic development, is that national governments are stood The requisite important content of method.Sulphur emissions is required very strict by industrially developed country, Federal Government Bureau for Environmental Protection Rules and regulations petroleum refining industry flue gas of heating furnace, tail gas of sulphur and regeneration fume from catalytic cracking SO2Concentration of emission limit value is 50ppm (v), about converts into 143mg/m3。
At present, China's sulfur recovery facility flue gas SO2Concentration of emission performs GB16297-1996, and " atmosphere pollution is comprehensively arranged Put standard ", standard regulation SO2Concentration of emission is less than 960mg/m3.The new environmental protection standard that will perform for 2014, it is stipulated that sulfur Retracting device flue gas SO2Concentration of emission is less than 400mg/m3, area discharge especially is less than 200mg/m3.Most domestic sulfur at present SO in sulphur retracting device flue gas2Though content is at 960mg/m3Hereinafter, but be difficult to reach 200mg/m3Standard-required.Affect sulfur dress Put flue gas SO2The factor of concentration of emission is mainly: cleaning of off-gas and the waste gas of molten sulfur degasification.
The total sulfur content of cleaning of off-gas is closely related with the conversion ratio of the degree of purification of desulfurizing agent and catalyst, cleaning of off-gas master To contain unabsorbed H2S and organic sulfur, be converted into SO after incinerator burns2, increase flue gas SO2Concentration of emission 150- 800mg/m3.If carrying out removing H to purifying gas2S process, purifies sulfide in gas and is down to below 10ppm, SO in flue gas2Concentration Will be remarkably decreased.At present, the purification gas of sulfur recovery facility typically directly enters incinerator and burns, and does not carry out other modes Desulfurization processes.The process of existing molten sulfur degasification waste gas uses incinerator incineration technology, and waste gas contains H2The sulfur-bearing things such as S and sulfur steam Matter is introduced directly into incinerator and processes, and sulphur-containing substance burning conversion is SO2, make flue gas SO2Concentration of emission increases 150-200mg/m3, The discharge standard that will implement cannot be met.
The U.S. has delivered the technique patent (US7311891B2) reclaiming sulfur by absorption method from Claus tail gas for 2007, will Containing SO2Tail gas by adsorbent bed, SO2It is adsorbed by adsorbent, is then desorbed SO by inert gas purge2, containing SO2Desorption Gas is recycled to Claus device and converts further.CN98114460.8 " processing method of a kind of industrial waste gas containing sulphur oxide " Described technical scheme, is the cleaning of off-gas absorbing out through absorption tower in sulfur recovery facility to be introduced directly into incinerator burn Burning, after burning, gas introducing catalysis oxidizing tower carries out oxidative absorption by SO2Become SO3, then by SO3With alkali liquor (Ca (OH)2Or Mg (OH)2) contact by-product gypsum.CN201010139106.1 " makes sulfur processed and the exhaust gas treating method of intermediate " of ammonium bisulfite Described technical scheme, for by the NH of sewage stripping unit in original recovery technology of sulfur3Separate and obtain gas ammonia or ammonia, then Tail gas (SO after burning2) introduce and wherein react, generate NH4HSO3(NH4)2SO3Claus reaction it is re-introduced into after atomization Stove reacts, and so circulates, cleaning of off-gas qualified discharge.
Summary of the invention
The technical problem to be solved is to provide a kind of recovery technology of sulfur reducing sulfur dioxide (SO2) emissions, effectively Reduce sulfur recovery facility SO2Concentration of emission, SO2Concentration of emission can realize being down to 100mg/m3Below.The method small investment, Operating cost is low, environmental protection and energy saving.
The recovery technology of sulfur of reduction sulfur dioxide (SO2) emissions of the present invention, including thermal response unit, catalytic reaction list Unit and cleaning of off-gas unit,
At thermal response unit, hydrogen sulfide containing sour gas divided combustion in the middle part of reacting furnace is converted into sulfur dioxide, at high temperature Lower hydrogen sulfide generates elementary sulfur and Process Gas with sulfur dioxide generation claus reaction, and elementary sulfur enters molten sulfur pond and obtains liquid sulfur Sulphur, Process Gas enters catalytic reaction unit；
Process Gas is at catalytic reaction unit after Crouse's catalyzed conversion, and elementary sulfur enters molten sulfur pond, reacted gram of labor This tail gas enters Tail gas cleanup unit；
First there is hydrogenation reaction at Tail gas cleanup unit in Claus tail gases in hydrogenation reactor, is converted into hydrogen sulfide, contains The hydrogenation tail gas of hydrogen sulfide is lowered the temperature through chilling tower, enters amine absorption tower, and the hydrogen sulfide in amine absorption hydrogenation tail gas, by amine liquid Tail gas after absorption introduces ammonia water tank to carry out removing hydrogen sulfide treatment, the ammonia after removing hydrogen sulfide is washed after-purification tail gas and introduces liquid Sulfur pond is as the gas stripping gas of molten sulfur degasification, and the waste gas of molten sulfur degasification is extracted out and mixed with Claus tail gases, and it is anti-that gaseous mixture enters hydrogenation Device is answered to process, or, the waste gas of molten sulfur degasification is mixed into catalytic reaction cell processing with Process Gas after extracting out, and remaining removes sulfur Change the ammonia after hydrogen and wash discharge after after-purification tail gas introducing incinerator burns.
Wherein:
Thermal response unit is by hydrogen sulfide containing sour gas and air mixed combustion in reacting furnace, controls ignition temperature 900-1400 DEG C, the sulfureted hydrogen burning of 1/3rd is converted into sulfur dioxide, and sulfur dioxide and hydrogen sulfide occur Claus to react, Generate elementary sulfur and containing hydrogen sulfide, sulfur dioxide and COS, CS2Process Gas.
2H2S+3O2→2SO2+2H2O (1)
SO2+ 2H2S→2H2O+3S (2)
Formed containing elementary sulfur, H2S、SO2With COS, CS2Process Gas.Elementary sulfur therein condensed entrance molten sulfur pond, Process Gas enters catalyst reaction section.
Catalytic reaction unit includes two-stage converter, filling claus catalyst, the reaction of one-level converter in converter Condition is: temperature 260-350 DEG C, air speed 400-1000h-1, the reaction bar of secondary reformer is: temperature 200-260 DEG C, air speed 400-1000h-1, under the effect of catalyst, occur to react as follows:
SO2+ 2H2S→2H2O+3S (3)
COS+H2O→H2S+CO2(4)
CS2+2H2O→2H2S+CO2(5)
After Crouse's catalyzed conversion, elementary sulfur condensed entrance molten sulfur pond, reacted Claus tail gases contains sulfuration Hydrogen, sulfur dioxide and COS, CS2Sulfides, enters Tail gas cleanup unit.
At Tail gas cleanup unit, Claus tail gases is heated to 200-300 DEG C of entrance hydrogenation reactor, in hydrogenation reactor Filling low temperature high activity hydrogenation catalyst, catalyst meets volume content H in Claus tail gases2S:0.1-5%, SO2: 0-1.5%, Organic sulfur: 0-0.5%, hydrogenation hydrolyzation conversion ratio reaches more than 99.9%.In hydrogenation reactor, the low temperature oxytolerant high activity of filling adds Hydrogen catalyst is preferably the commercially available prod LSH-03 that Shandong Qilu Keli Chemical Research Institute Co., Ltd. produces.At hydrogenation catalyst Effect under, the elementary sulfur that carries in tail gas, SO2It is completely converted into H Deng hydrogenation2S, COS, CS2Hydrolysis is H2S.Containing H2S's Hydrogenation tail gas is cooled to 25-42 DEG C through chilling tower, enters filling desulfurizing agent in amine absorption tower, amine absorption tower, commercially available desulfurization Agent all can meet requirement, preferably MDEA.H2S, by amine absorption, absorbs H2Cleaning of off-gas H after S2S content typically arrives tens Hundreds of ppm (v)；Cleaning of off-gas is introduced ammonia water tank, reacts below generation in ammonia water tank:
H2S+2NH4OH → (NH4)2S+2H2O
NH4OH+H2S→NH4HS+H2O
In ammonia water tank, purify the H in gas2S and ammonia react and generate sulfur hydrogenation ammonia or sulfuration ammonia, make in purification gas H2S content is less than 5mg/m3Below.Containing only not on a small quantity being hydrolyzed in catalytic converter in cleaning of off-gas after ammonia absorption Organic sulfur and the H of trace2S, will remove H2Ammonia after S is washed after-purification gas and is introduced the molten sulfur pond gas stripping gas as molten sulfur degasification, molten sulfur The waste gas of degassing is extracted out and is mixed with Claus tail gas, and gaseous mixture enters hydrogenation reactor and processes；Or, the waste gas of molten sulfur degasification is taken out It is mixed into one with Process Gas be mixed into the waste gas extraction of catalytic reaction cell processing, i.e. molten sulfur degasification after going out with Process Gas after Level converter or secondary reformer process；Remaining ammonia is washed after-purification tail gas and is introduced discharge after incinerator burns.Amine absorption tower is even Connect amine liquid regenerator, absorb H2The amine liquid (rich amine solution) of S enters regenerator and regenerates, and regenerated acidic gas mixes with sour gas, Return to thermal response unit and reclaim elementary sulfur further.By using this technique, H in cleaning of off-gas2S content can be less than 5mg/m3, sulfur recovery facility flue gas SO2Concentration of emission is less than 100mg/m3。
After ammonia uses certain time, assimilation effect can be deteriorated, and needs periodic replacement, and the deposed ammonia after ammonia water tank uses is delivered to Hydrogen sulfide and ammonia are stripped off by sewage stripping device.
Deposed ammonia is delivered to sulfur-containing sewage stripping device and is processed, and sulfur-containing sewage stripping device utilizes steam waving in sewage The H of the property sent out2S and NH3It is stripped off from sewage respectively, can be by sewage purification and extract H respectively2S and ammonia.Whole process can Represent by following combined reaction formula:
OH-+H++NH4+HS-=(NH3+H2S+H2O)Liquid=(NH3+H2S+H2O)Gas
The H extracted2S returns sulfur recovery facility and carries out sulfur recovery, and the ammonia extracted returns ammonia water tank circulation profit With.
Deposed ammonia can be delivered to sulfur-containing sewage stripping device and regenerate, and can be recycled after regeneration.If do not considered, ammonia follows Ring regenerates, and uses other kind alkali liquor also can meet requirement.If ammonia concn is too low, ammonia compares high with purifying air volume, Plant running energy consumption is higher；During the too high plant running of ammonia concn volatile, a certain amount of liquefied ammonia can be caused to lose, so Ammonia concn is generally 5%-25%, preferably 10%-15%.The absorption temperature of ammonia water tank is generally room temperature, purifies gas and ammonia Water volume ratio is 1-600:1.Ensure de-after-purification tail gas H2S content is less than 5mg/m3。
In tail gas treating unit of the present invention, the processing method of the waste gas of molten sulfur degasification is: it mixed with Claus tail gases, Gaseous mixture enter hydrogenation reactor process, the hydrogenated hydrogen sulfide that is converted into of sulfur vapor in gas, hydrogen sulfide through amine absorption, regeneration, Return sulfur stove processed and reclaim elementary sulfur.Or, the waste gas of molten sulfur degasification is mixed into one-level converter or two with Process Gas after extracting out Level converter, i.e. catalytic reaction cell processing, carrys out Recovered sulphur.
When molten sulfur degasification waste gas introduces hydrogenation reactor process, described Claus catalyzer for hydrogenation on tail gas is that low temperature is high Active hydrofining catalyst, relatively typical catalyst activity improves more than 30%.Molten sulfur degasification waste gas need not heating, direct and Claus Tail gas mixes, and hydrogenation reactor inlet temperature controls 220-300 DEG C, and catalyst should have deoxidation, tempreture organic sulphur hydrolysis, SO simultaneously2 With the several functions such as S hydrogenation, it is ensured that the sulphur-containing substance of unvulcanised hydrogen moment hydrogenation or hydrolysis in 3 seconds are hydrogen sulfide, keep away Exempt from sulfur penetration phenomenon to occur.
The present invention is applicable to existing or newly-built Claus+SCOT sulfur recovery unit flue gas SO2Discharge upgrading.At traditional gram On the basis of+SCOT the tail gas treatment process of Louth, add ammonia absorption tank, in ammonia absorption tank, cleaning of off-gas is removed H2S, it is ensured that H in cleaning of off-gas2S content is less than 5mg/m3；Deposed ammonia processes to sewage stripping device, can at sewage stripping device Extract H respectively2S and ammonia, the H extracted2S returns sulfur recovery facility and carries out sulfur recovery, and the ammonia extracted returns ammonia Tank recycles；Sulfur recovery unit molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used for sulphur unit ammonia absorption After cleaning of off-gas；Introduce hydrogenation reactor after its molten sulfur degasification waste gas and the mixing of Claus tail gas to process, its reactor filling height Active hydrofining catalyst.After hydrogenation, tail gas passes through chilling, amine absorption cleaning, discharged in burning, final sulphur unit flue gas SO2Discharge Concentration can be down to 100mg/m3Hereinafter, meet the new environmental protection standard that will perform, solve the discharge of existing sulphur unit the most up to standard Realistic problem, provide a kind of small investment, new method that operating cost is low for newly-built sulphur unit.
Using ammonia absorption to process sulfur recovery facility cleaning of off-gas and have good absorbing effect, simple to operate, expense is low Feature, deposed ammonia is delivered to sewage stripping device and is processed, can extract H respectively at sewage stripping device2S and ammonia, extract H2S returns sulfur recovery facility and carries out sulfur recovery, the ammonia that extracts returns ammonia ammonia circulation and utilizes, and has environmental protection, saving Feature.By the process to sulfur recovery facility cleaning of off-gas, it is ensured that H in tail gas2S content is less than 5mg/m3, final sulphur recovery Device flue gas SO2Concentration of emission can significantly reduce, and has significant environmental benefit.
Compared to existing technology, the present invention has the advantage that
(1) providing the recovery technology of sulfur reducing sulfur dioxide (SO2) emissions of a kind of less expensive, this technique can will purify tail H in gas2S is removed to 5mg/m3Hereinafter, SO in flue gas2Content can be down to 100mg/m3Hereinafter, the amplitude that reduces is typically at 100- 800mg/m3Between, meet the new environmental protection standard that will perform；
(2) using ammonia absorption to process sulfur recovery facility cleaning of off-gas makes hydrogen sulfide be absorbed further, has absorption Effective, simple to operate, advantage that expense is low, it is provided that the processing method of deposed ammonia, deposed ammonia to sewage stripping device processes, H can be extracted respectively at sewage stripping device2S and ammonia, the H extracted2S returns sulfur recovery facility and carries out sulfur recovery, extracts Ammonia out returns ammonia water tank and recycles, the advantage with environmental protection, saving；
(3) providing a kind of environmental protection, the processing method of energy-conservation molten sulfur degasification waste gas, sulphur-containing exhaust gas introduces hydrogenation reactor Or sulfur converter processed processes, it is to avoid be directly entered incinerator and burn and affect fume emission；
(4) a kind of method providing molten sulfur degasification, uses cleaning of off-gas bubble techniques, has saved the use of nitrogen, steam Amount.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of any embodiment in embodiment of the present invention 1-5；
Fig. 2 is the process flow diagram of the embodiment of the present invention 6；
Fig. 3 is the process flow diagram of the embodiment of the present invention 7；
Fig. 4 is the process chart of prior art.
In figure: 1-sour gas；2-reacting furnace；3-one-level converter；4-secondary reformer；5-Claus tail gas；6-hydrogenation is anti- Answer device；7-chilling tower；8-amine absorption tower；9-cleaning of off-gas；10-molten sulfur degasification waste gas；11-molten sulfur pond；12-incinerator；13- Regenerator；14-regenerated acidic gas；15-lean solution；16-ammonia water tank；17-sewage stripping device；18-ammonia washes after-purification tail gas；19- Ammonia；20-air or nitrogen.
Detailed description of the invention
Embodiment 1:
Technological process is as shown in Figure 1.This technique contains thermal response section, catalyst reaction section and tail gas clean-up processing section.
Thermal response Duan Weihan H2S about 92(v/v) sour gas 1 divided combustion in the middle part of reacting furnace 2 of % is converted into SO2, 1250 DEG C high temperature under H2S and SO2Claus reaction is occurred to generate elementary sulfur and Process Gas.Process Gas sulfur-containing compound volume content is: H2S:5.8%, SO2: 2.6%, organic sulfur: 0.5%.
The one-level converter 3(reaction condition of Process Gas entrance catalyst reaction section: temperature 310 DEG C, air speed 800h-1) and two grades Converter 4(reaction condition: temperature 245 DEG C, air speed 800h-1), after Claus catalyzed conversion, reacted Claus tail gas 5 enters Enter Tail gas cleanup unit.Claus tail gas sulfur-containing compound volume content is: H2S:2.9%, SO2: 1.3%, organic sulfur: 0.1%.
Claus tail gas is in hydrogenation reactor 6 under the effect of hydrogenation catalyst, and sulfur-containing compound hydro-conversion is H2S, so It is cooled to 40 DEG C by chilling tower 7, enters amine absorption tower 8；H in amine absorption hydrogenation tail gas2S, clean after making amine absorption Change H in tail gas 92S content is down to 112ppm (v), and cleaning of off-gas 9 introduces ammonia water tank 16, and in ammonia water tank 16, ammonia concn is 10%, the absorption temperature of ammonia water tank 16 is 25 DEG C, and purifying gas with ammonia volume ratio is 300:1, and ammonia washes after-purification tail gas 18H2S contains Amount is 2mg/m3.Molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used to be washed after cure hydrogen content for sulphur unit ammonia and be 2mg/m3Ammonia wash after-purification tail gas 18, introduce at hydrogenation reactor 6 after the mixing of its molten sulfur degasification waste gas 10 and Claus tail gas 5 Reason, its hydrogenation reactor uses the high-activity hydrogenation catalyst LSH-03 of Sinopec asphalt in Shenli Refinery academy exploitation, protects Card deoxidation and tempreture organic sulphur hydrolysis effect.Ammonia after remaining removing hydrogen sulfide is washed after-purification tail gas 18 and is introduced incinerator 12 and burn heel row Put.Amine absorption tower 8 connects amine liquid regenerator 13, absorbs H2The amine liquid (rich amine solution) of S enters regenerator 13 and regenerates, regeneration Sour gas 14 mixes with sour gas 1, returns to thermal response unit and reclaims elementary sulfur further.The deposed ammonia of ammonia water tank 16 is delivered to Sewage stripping device 17 processes, and extracts H respectively at sewage stripping device 172S and ammonia, the H extracted2S returns sulphur recovery Device carries out sulfur recovery, and the ammonia extracted returns ammonia water tank and recycles.Sulphur unit flue gas SO2Concentration of emission 42mg/m3, Far below the environmental regulation that will implement.
Embodiment 2:
Technological process is as shown in Figure 1.This technique contains thermal response section, catalyst reaction section and tail gas clean-up processing section.
Thermal response Duan Weihan H2S about 82(v/v) sour gas 1 divided combustion in the middle part of reacting furnace 2 of % is converted into SO2, 1250 DEG C high temperature under H2S and SO2Claus reaction is occurred to generate elementary sulfur and Process Gas.Process Gas sulfur-containing compound volume content is: H2S:5.6%, SO2: 2.4%, organic sulfur: 0.4%.
The one-level converter 3(reaction condition of Process Gas entrance catalyst reaction section: temperature 300 DEG C, air speed 800h-1) and two grades Converter 4(reaction condition: temperature 250 DEG C, air speed 800h-1), after Claus catalyzed conversion, reacted Claus tail gas 5 enters Enter Tail gas cleanup unit.Claus tail gas sulfur-containing compound volume content is: H2S:2.7%, SO2: 1.3%, organic sulfur: 0.09%.
Claus tail gas is in hydrogenation reactor 6 under the effect of hydrogenation catalyst, and sulfur-containing compound hydro-conversion is H2S, so It is cooled to 40 DEG C by chilling tower 7, enters amine absorption tower 8；H in amine absorption hydrogenation tail gas2S, clean after making amine absorption Change H in tail gas 92S content is down to 78ppm (v), and cleaning of off-gas 9 introduces ammonia water tank 16, and in ammonia water tank 16, ammonia concn is 15%, the absorption temperature of ammonia water tank 16 is 25 DEG C, and purifying gas with ammonia volume ratio is 300:1, and ammonia washes after-purification tail gas 18H2S contains Amount is 1mg/m3.Molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used to be washed after cure hydrogen content for sulphur unit ammonia and be 1mg/m3Ammonia wash after-purification tail gas 18, introduce at hydrogenation reactor 6 after the mixing of its molten sulfur degasification waste gas 10 and Claus tail gas 5 Reason, its hydrogenation reactor uses the high-activity hydrogenation catalyst LSH-03 of Sinopec asphalt in Shenli Refinery academy exploitation, protects Card deoxidation and tempreture organic sulphur hydrolysis effect.Ammonia after remaining removing hydrogen sulfide is washed after-purification tail gas 18 and is introduced incinerator 12 and burn heel row Put.Amine absorption tower 8 connects amine liquid regenerator 13, absorbs H2The amine liquid (rich amine solution) of S enters regenerator 13 and regenerates, regeneration Sour gas 14 mixes with sour gas 1, returns to thermal response unit and reclaims elementary sulfur further.The deposed ammonia of ammonia water tank 16 is delivered to Sewage stripping device 17 processes, and extracts H respectively at sewage stripping device 172S and ammonia, the H extracted2S returns sulphur recovery Device carries out sulfur recovery, and the ammonia extracted returns ammonia water tank and recycles.Sulphur unit flue gas SO2Concentration of emission 40mg/m3, Far below the environmental regulation that will implement.
Embodiment 3:
Technological process is as shown in Figure 1.This technique contains thermal response section, catalyst reaction section and tail gas clean-up processing section.
Thermal response Duan Weihan H2S about 82(v/v) sour gas 1 divided combustion in the middle part of reacting furnace 2 of % is converted into SO2, 1250 DEG C high temperature under H2S and SO2Claus reaction is occurred to generate elementary sulfur and Process Gas.Process Gas sulfur-containing compound volume content is: H2S:5.6%, SO2: 2.4%, organic sulfur: 0.4%.
The one-level converter 3(reaction condition of Process Gas entrance catalyst reaction section: temperature 300 DEG C, air speed 800h-1) and two grades Converter 4(reaction condition: temperature 250 DEG C, air speed 800h-1), after Claus catalyzed conversion, reacted Claus tail gas 5 enters Enter Tail gas cleanup unit.Claus tail gas sulfur-containing compound volume content is: H2S:2.7%, SO2: 1.3%, organic sulfur: 0.09%.
Claus tail gas is in hydrogenation reactor 6 under the effect of hydrogenation catalyst, and sulfur-containing compound hydro-conversion is H2S, so It is cooled to 40 DEG C by chilling tower 7, enters amine absorption tower 8；H in amine absorption hydrogenation tail gas2S, clean after making amine absorption Change H in tail gas 92S content is down to 78ppm (v), and cleaning of off-gas 9 introduces ammonia water tank 16, and in ammonia water tank 16, ammonia concn is 5%, The absorption temperature of ammonia water tank 16 is 25 DEG C, and purifying gas with ammonia volume ratio is 600:1, and ammonia washes after-purification tail gas 18H2S content is 4mg/m3.Molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used, and to wash after cure hydrogen content for sulphur unit ammonia be 4mg/m3 Ammonia wash after-purification tail gas 18, its molten sulfur degasification waste gas 10 and Claus tail gas 5 mixing after introduce hydrogenation reactor 6 process, it adds Hydrogen reactor use Sinopec asphalt in Shenli Refinery academy exploitation high-activity hydrogenation catalyst LSH-03, ensure deoxidation and Tempreture organic sulphur hydrolysis effect.Ammonia after remaining removing hydrogen sulfide is washed after-purification tail gas 18 and is introduced discharge after incinerator 12 burns.Amine liquid Absorption tower 8 connects amine liquid regenerator 13, absorbs H2The amine liquid (rich amine solution) of S enters regenerator 13 and regenerates, regenerated acidic gas 14 mix with sour gas 1, return to thermal response unit and reclaim elementary sulfur further.The deposed ammonia of ammonia water tank 16 delivers to sewage vapour Carry device 17 to process, extract H respectively at sewage stripping device 172S and ammonia, the H extracted2S returns sulfur recovery facility and enters Row sulfur recovery, the ammonia extracted returns ammonia water tank and recycles.Sulphur unit flue gas SO2Concentration of emission 46mg/m3, it is far below The environmental regulation that will implement.
Embodiment 4:
Technological process is as shown in Figure 1.This technique contains thermal response section, catalyst reaction section and tail gas clean-up processing section.
Thermal response Duan Weihan H2S about 82(v/v) sour gas 1 divided combustion in the middle part of reacting furnace 2 of % is converted into SO2, 1250 DEG C high temperature under H2S and SO2Claus reaction is occurred to generate elementary sulfur and Process Gas.Process Gas sulfur-containing compound volume content is: H2S:5.6%, SO2: 2.4%, organic sulfur: 0.4%.
The one-level converter 3(reaction condition of Process Gas entrance catalyst reaction section: temperature 300 DEG C, air speed 800h-1) and two grades Converter 4(reaction condition: temperature 250 DEG C, air speed 800h-1), after Claus catalyzed conversion, reacted Claus tail gas 5 enters Enter Tail gas cleanup unit.Claus tail gas sulfur-containing compound volume content is: H2S:2.7%, SO2: 1.3%, organic sulfur: 0.09%.
Claus tail gas is in hydrogenation reactor 6 under the effect of hydrogenation catalyst, and sulfur-containing compound hydro-conversion is H2S, so It is cooled to 40 DEG C by chilling tower 7, enters amine absorption tower 8；H in amine absorption hydrogenation tail gas2S, clean after making amine absorption Change H in tail gas 92S content is down to 78ppm (v), and cleaning of off-gas 9 introduces ammonia water tank 16, and in ammonia water tank 16, ammonia concn is 10%, the absorption temperature of ammonia water tank 16 is 25 DEG C, and purifying gas with ammonia volume ratio is 100:1, and ammonia washes after-purification tail gas 18H2S contains Amount is 4mg/m3.Molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used to be washed after cure hydrogen content for sulphur unit ammonia and be 4mg/m3Ammonia wash after-purification tail gas 18, introduce at hydrogenation reactor 6 after the mixing of its molten sulfur degasification waste gas 10 and Claus tail gas 5 Reason, its hydrogenation reactor uses the high-activity hydrogenation catalyst LSH-03 of Sinopec asphalt in Shenli Refinery academy exploitation, protects Card deoxidation and tempreture organic sulphur hydrolysis effect.Ammonia after remaining removing hydrogen sulfide is washed after-purification tail gas 18 and is introduced incinerator 12 and burn heel row Put.Amine absorption tower 8 connects amine liquid regenerator 13, absorbs H2The amine liquid (rich amine solution) of S enters regenerator 13 and regenerates, regeneration Sour gas 14 mixes with sour gas 1, returns to thermal response unit and reclaims elementary sulfur further.The deposed ammonia of ammonia water tank 16 is delivered to Sewage stripping device 17 processes, and extracts H respectively at sewage stripping device 172S and ammonia, the H extracted2S returns sulphur recovery Device carries out sulfur recovery, and the ammonia extracted returns ammonia water tank circulation.Sulphur unit flue gas SO2Concentration of emission 47mg/m3, the lowest In the environmental regulation that will implement.
Embodiment 5:
Technological process is as shown in Figure 1.This technique contains thermal response section, catalyst reaction section and tail gas clean-up processing section.
Thermal response Duan Weihan H2S about 82(v/v) sour gas 1 divided combustion in the middle part of reacting furnace 2 of % is converted into SO2, 1250 DEG C high temperature under H2S and SO2Claus reaction is occurred to generate elementary sulfur and Process Gas.Process Gas sulfur-containing compound volume content is: H2S:5.6%, SO2: 2.4%, organic sulfur: 0.4%.
The one-level converter 3(reaction condition of Process Gas entrance catalyst reaction section: temperature 300 DEG C, air speed 800h-1) and two grades Converter 4(reaction condition: temperature 250 DEG C, air speed 800h-1), after Claus catalyzed conversion, reacted Claus tail gas 5 enters Enter Tail gas cleanup unit.Claus tail gas sulfur-containing compound volume content is: H2S:2.7%, SO2: 1.3%, organic sulfur: 0.09%.
Claus tail gas is in hydrogenation reactor 6 under the effect of hydrogenation catalyst, and sulfur-containing compound hydro-conversion is H2S, so It is cooled to 40 DEG C by chilling tower 7, enters amine absorption tower 8；H in amine absorption hydrogenation tail gas2S, clean after making amine absorption Change H in tail gas 92S content is down to 78ppm (v), and cleaning of off-gas 9 introduces ammonia water tank 16, and in ammonia water tank 16, ammonia concn is 5%, The absorption temperature of ammonia water tank 16 is 25 DEG C, and purifying gas with ammonia volume ratio is 10:1, and ammonia washes after-purification tail gas 18H2S content is 1mg/m3.Molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used, and to wash after cure hydrogen content for sulphur unit ammonia be 1mg/m3 Ammonia wash after-purification tail gas 18, its molten sulfur degasification waste gas 10 and Claus tail gas 5 mixing after introduce hydrogenation reactor 6 process, it adds Hydrogen reactor use Sinopec asphalt in Shenli Refinery academy exploitation high-activity hydrogenation catalyst LSH-03, ensure deoxidation and Tempreture organic sulphur hydrolysis effect.Ammonia after remaining removing hydrogen sulfide is washed after-purification tail gas 18 and is introduced discharge after incinerator 12 burns.Amine liquid Absorption tower 8 connects amine liquid regenerator 13, absorbs H2The amine liquid (rich amine solution) of S enters regenerator 13 and regenerates, regenerated acidic gas 14 mix with sour gas 1, return to thermal response unit and reclaim elementary sulfur further.The deposed ammonia of ammonia water tank 16 delivers to sewage vapour Carry device 17 to process, extract H respectively at sewage stripping device 172S and ammonia, the H extracted2S returns sulfur recovery facility and enters Row sulfur recovery, the ammonia extracted returns ammonia water tank and recycles.Sulphur unit flue gas SO2Concentration of emission 38mg/m3, it is far below The environmental regulation that will implement.
Embodiment 6:
Technological process is as shown in Figure 2.This technique contains thermal response section, catalyst reaction section and tail gas clean-up processing section.
Thermal response Duan Weihan H2S about 82(v/v) sour gas 1 divided combustion in the middle part of reacting furnace 2 of % is converted into SO2, 1250 DEG C high temperature under H2S and SO2Claus reaction is occurred to generate elementary sulfur and Process Gas.Process Gas sulfur-containing compound volume content is: H2S:5.6%, SO2: 2.4%, organic sulfur: 0.4%.
The one-level converter 3(reaction condition of Process Gas entrance catalyst reaction section: temperature 300 DEG C, air speed 800h-1) and two grades Converter 4(reaction condition: temperature 250 DEG C, air speed 800h-1), after Claus catalyzed conversion, reacted Claus tail gas 5 enters Enter Tail gas cleanup unit.Claus tail gas sulfur-containing compound volume content is: H2S:2.7%, SO2: 1.3%, organic sulfur: 0.09%.
Claus tail gas is in hydrogenation reactor 6 under the effect of hydrogenation catalyst, and sulfur-containing compound hydro-conversion is H2S, so It is cooled to 40 DEG C by chilling tower 7, enters amine absorption tower 8；H in amine absorption hydrogenation tail gas2S, clean after making amine absorption Change H in tail gas 92S content is down to 78ppm (v), and cleaning of off-gas 9 introduces ammonia water tank 16, and in ammonia water tank 16, ammonia concn is 15%, the absorption temperature of ammonia water tank 16 is 25 DEG C, and purifying gas with ammonia volume ratio is 1:1, and ammonia washes after-purification tail gas 18H2S content For 1mg/m3.Molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used to be washed after cure hydrogen content for sulphur unit ammonia and be 1mg/m3Ammonia wash after-purification tail gas 18, its molten sulfur degasification waste gas 10 and Process Gas mixing after introduce one-level converter 3 process.Its Ammonia after remaining removing hydrogen sulfide is washed after-purification tail gas 18 and is introduced discharge after incinerator 12 burns.Amine absorption tower 8 connects amine liquid again Raw tower 13, absorbs H2The amine liquid (rich amine solution) of S enters regenerator 13 and regenerates, and regenerated acidic gas 14 mixes with sour gas 1, weight The new thermal response unit that returns reclaims elementary sulfur further.The deposed ammonia of ammonia water tank 16 is delivered to sewage stripping device 17 and is processed, in dirt Water stripper plant 17 extracts H respectively2S and ammonia, the H extracted2S returns sulfur recovery facility and carries out sulfur recovery, extracts Ammonia return ammonia water tank recycle.Sulphur unit flue gas SO2Concentration of emission 41mg/m3, far below the environmental law that will implement Rule.
Embodiment 7:
Technological process is as shown in Figure 3.This technique contains thermal response section, catalyst reaction section and tail gas clean-up processing section.
Thermal response Duan Weihan H2S about 82(v/v) sour gas 1 divided combustion in the middle part of reacting furnace 2 of % is converted into SO2, 1250 DEG C high temperature under H2S and SO2Claus reaction is occurred to generate elementary sulfur and Process Gas.Process Gas sulfur-containing compound volume content is: H2S:5.6%, SO2: 2.4%, organic sulfur: 0.4%.
The one-level converter 3(reaction condition of Process Gas entrance catalyst reaction section: temperature 300 DEG C, air speed 800h-1) and two grades Converter 4(reaction condition: temperature 250 DEG C, air speed 800h-1), after Claus catalyzed conversion, reacted Claus tail gas 5 enters Enter Tail gas cleanup unit.Claus tail gas sulfur-containing compound volume content is: H2S:2.7%, SO2: 1.3%, organic sulfur: 0.09%.
Claus tail gas is in hydrogenation reactor 6 under the effect of hydrogenation catalyst, and sulfur-containing compound hydro-conversion is H2S, so It is cooled to 40 DEG C by chilling tower 7, enters amine absorption tower 8；H in amine absorption hydrogenation tail gas2S, clean after making amine absorption Change H in tail gas 92S content is down to 78ppm (v), and cleaning of off-gas 9 introduces ammonia water tank 16, and in ammonia water tank 16, ammonia concn is 15%, the absorption temperature of ammonia water tank 16 is 25 DEG C, and purifying gas with ammonia volume ratio is 200:1, and ammonia washes after-purification tail gas 18H2S contains Amount is 1mg/m3.Molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used to be washed after cure hydrogen content for sulphur unit ammonia and be 1mg/m3Ammonia wash after-purification tail gas 18, its molten sulfur degasification waste gas 10 and Process Gas mixing after introduce secondary reformer 4 process.Its Ammonia after remaining removing hydrogen sulfide is washed after-purification tail gas 18 and is introduced discharge after incinerator 12 burns.Amine absorption tower 8 connects amine liquid again Raw tower 13, absorbs H2The amine liquid (rich amine solution) of S enters regenerator 13 and regenerates, and regenerated acidic gas 14 mixes with sour gas 1, weight The new thermal response unit that returns reclaims elementary sulfur further.The useless ammoniacal liquor of ammonia water tank 16 is delivered to sewage stripping device 17 and is processed, in dirt Water stripper plant 17 extracts H respectively2S and ammonia, the H extracted2S returns sulfur recovery facility and carries out sulfur recovery, extracts Ammonia return ammonia water tank recycle.Sulphur unit flue gas SO2Concentration of emission 42mg/m3, far below the environmental law that will implement Rule.
Comparative example 1:
Technological process is as shown in Figure 4.This technique contains thermal response section, catalyst reaction section and tail gas clean-up processing section.
Thermal response Duan Weihan H2S about 92(v/v) sour gas 1 divided combustion in the middle part of reacting furnace 2 of % is converted into SO2, 1250 DEG C high temperature under H2S and SO2Claus reaction is occurred to generate elementary sulfur and Process Gas.Process Gas sulfur-containing compound volume content is: H2S:5.8%, SO2: 2.6%, organic sulfur: 0.5%.
The one-level converter 3(reaction condition of Process Gas entrance catalyst reaction section: temperature 310 DEG C, air speed 800h-1) and two grades Converter 4(reaction condition: temperature 245 DEG C, air speed 800h-1), after Claus catalyzed conversion, reacted Claus tail gas 5 enters Enter Tail gas cleanup unit.Claus tail gas sulfur-containing compound volume content is: H2S:2.9%, SO2: 1.3%, organic sulfur: 0.1%.
Claus tail gas is in hydrogenation reactor 6 under the effect of hydrogenation catalyst, and sulfur-containing compound hydro-conversion is H2S, so It is cooled to 40 DEG C by chilling tower 7, enters amine absorption tower 8；H in amine absorption hydrogenation tail gas2S, makes purification gas 12H2S contains Amount is down to 112ppm (v), and purification gas 12 is introduced directly into incinerator 10 burning disposal, and after process, flue gas is directly discharged into through chimney 11 Air, purifies H in gas2S is all converted into SO after burning2.Molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used is outward For air or nitrogen, degassing waste gas mixes with cleaning of off-gas, discharges after incinerator burns.Use this technique, the flue gas of discharge Middle SO2Concentration is 723mg/m3。
Comparative example 2
Technological process is as shown in Figure 4.This technique contains thermal response section, catalyst reaction section and tail gas clean-up processing section.
Thermal response Duan Weihan H2S about 82(v/v) sour gas 1 divided combustion in the middle part of reacting furnace 2 of % is converted into SO2, 1250 DEG C high temperature under H2S and SO2Claus reaction is occurred to generate elementary sulfur and Process Gas.Process Gas sulfur-containing compound volume content is: H2S:5.6%, SO2: 2.4%, organic sulfur: 0.4%.
The one-level converter 3(reaction condition of Process Gas entrance catalyst reaction section: temperature 300 DEG C, air speed 800h-1) and two grades Converter 4(reaction condition: temperature 250 DEG C, air speed 800h-1), after Claus catalyzed conversion, reacted Claus tail gas 5 enters Enter Tail gas cleanup unit.Claus tail gas sulfur-containing compound volume content is: H2S:2.7%, SO2: 1.3%, organic sulfur: 0.09%.
Claus tail gas is in hydrogenation reactor 6 under the effect of hydrogenation catalyst, and sulfur-containing compound hydro-conversion is H2S, so It is cooled to 40 DEG C by chilling tower 7, enters amine absorption tower 8；H in amine absorption hydrogenation tail gas2S, makes purification gas 12H2S contains Amount is down to 78ppm (v), and purification gas 12 is introduced directly into incinerator 10 burning disposal, and after process, flue gas is directly discharged into through chimney 11 Air, purifies H in gas2S is all converted into SO after burning2.Molten sulfur degasification mode uses bubbling to deaerate, and bubbling is gases used is outward For air or nitrogen, degassing waste gas mixes with cleaning of off-gas, discharges after incinerator burns.Use this technique, the flue gas of discharge Middle SO2Concentration is 629mg/m3。
Embodiment Molten sulfur degasification exhaust-gas treatment mode SO in flue gas2Concentration
Embodiment 1 Enter hydrogenation reactor to process 42mg/m3
Embodiment 2 Enter hydrogenation reactor to process 40mg/m3
Embodiment 3 Enter hydrogenation reactor to process 46mg/m3
Embodiment 4 Enter hydrogenation reactor to process 47mg/m3
Embodiment 5 Enter hydrogenation reactor to process 38mg/m3
Embodiment 6 Enter one-level converter to process 41mg/m3
Embodiment 7 Enter secondary reformer to process 42mg/m3
Comparative example 1 Directly burn 723mg/m3
Comparative example 2 Directly burn 629mg/m3

Claims (9)

1. reduce a recovery technology of sulfur for sulfur dioxide (SO2) emissions, including thermal response unit, catalytic reaction unit and purification tail Gas unit, it is characterised in that:
At thermal response unit, hydrogen sulfide containing sour gas divided combustion in the middle part of reacting furnace is converted into sulfur dioxide, at high temperature sulfur Changing hydrogen and generate elementary sulfur and Process Gas with sulfur dioxide generation claus reaction, elementary sulfur enters molten sulfur pond and obtains Molten sulphur, Process Gas enters catalytic reaction unit；
Process Gas is at catalytic reaction unit after Crouse's catalyzed conversion, and elementary sulfur enters molten sulfur pond, reacted Crouse's tail Gas enters Tail gas cleanup unit；
First there is hydrogenation reaction at Tail gas cleanup unit in Claus tail gases in hydrogenation reactor, is converted into hydrogen sulfide, Containing Sulfur The hydrogenation tail gas of hydrogen is lowered the temperature through chilling tower, enters amine absorption tower, and the hydrogen sulfide in amine absorption hydrogenation tail gas, by amine absorption After cleaning of off-gas introduce ammonia water tank carry out remove hydrogen sulfide treatment, will removing hydrogen sulfide after ammonia wash after-purification tail gas introduce liquid Sulfur pond is as the gas stripping gas of molten sulfur degasification, and the waste gas of molten sulfur degasification is extracted out and mixed with Claus tail gases, and it is anti-that gaseous mixture enters hydrogenation Device is answered to process, or, the waste gas of molten sulfur degasification is mixed into catalytic reaction cell processing with Process Gas after extracting out, and remaining removes sulfur Change the ammonia after hydrogen and wash discharge after after-purification tail gas introducing incinerator burns；
Deposed ammonia after ammonia water tank uses is delivered to hydrogen sulfide and ammonia are stripped off in sewage stripping device, extracts again Raw sour gas returns to sulfur recovery facility and carries out sulfur recovery, and the ammonia extracted returns ammonia water tank and recycles.
The recovery technology of sulfur of reduction sulfur dioxide (SO2) emissions the most according to claim 1, it is characterised in that: thermal response unit It is by hydrogen sulfide containing sour gas and air mixed combustion in reacting furnace, controls ignition temperature 900-1400 DEG C, 1/3rd Sulfureted hydrogen burning be converted into sulfur dioxide, sulfur dioxide and hydrogen sulfide occur Claus react, generate elementary sulfur and contain sulfur Change hydrogen, sulfur dioxide and COS, CS2Process Gas.
The recovery technology of sulfur of reduction sulfur dioxide (SO2) emissions the most according to claim 1, it is characterised in that: catalytic reaction list Unit includes two-stage converter, and filling claus catalyst in converter, the reaction condition of one-level converter is: temperature 260-350 DEG C, air speed 400-1000h-1, the reaction bar of secondary reformer is: temperature 200-260 DEG C, air speed 400-1000h-1, through Crouse After catalyzed conversion, elementary sulfur condensed entrance molten sulfur pond, reacted Claus tail gases contain hydrogen sulfide, sulfur dioxide and COS, CS2Sulfide.
The recovery technology of sulfur of reduction sulfur dioxide (SO2) emissions the most according to claim 1, it is characterised in that: at tail gas clean-up Unit, Claus tail gases is heated to 200-300 DEG C of entrance hydrogenation reactor, and hydrogen sulfide containing hydrogenation tail gas is lowered the temperature through chilling tower To 25-42 DEG C, subsequently into amine absorption tower.
The recovery technology of sulfur of reduction sulfur dioxide (SO2) emissions the most according to claim 1, it is characterised in that: hydrogenation reactor Interior filling low temperature high activity hydrogenation catalyst, catalyst meets volume content H in Claus tail gases2S:0.1-5%, SO2:0- 1.5%, organic sulfur: 0-0.5%, hydrogenation hydrolyzation conversion ratio reaches more than 99.9%.
The recovery technology of sulfur of reduction sulfur dioxide (SO2) emissions the most according to claim 5, it is characterised in that: hydrogenation reactor The low temperature high activity hydrogenation catalyst of interior filling is the commercially available prod that Shandong Qilu Keli Chemical Research Institute Co., Ltd. produces LSH-03。
The recovery technology of sulfur of reduction sulfur dioxide (SO2) emissions the most according to claim 1, it is characterised in that: amine absorption tower Connecting amine liquid regenerator, the amine liquid absorbing hydrogen sulfide enters regenerator regeneration, and regenerated acidic gas returns to thermal response unit.
The recovery technology of sulfur of reduction sulfur dioxide (SO2) emissions the most according to claim 1, it is characterised in that: ammonia in ammonia water tank The concentration of water is 5-25%.
The recovery technology of sulfur of reduction sulfur dioxide (SO2) emissions the most according to claim 1, it is characterised in that: the suction of ammonia water tank Shrinkage temperature is room temperature, and the volume ratio purifying gas and ammonia is 1-600:1.
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Application publication date: 20150429

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